Rh nanoclusters encaged in hollow mesoporous silica nanoreactors with enhanced catalytic performance for phenol selective hydrogenation

Here, we report the synthesis of Rh nanoclusters (~0.8 nm) encapsulated in hollow mesoporous silica nanoreactors ([email protected]) for phenol selective hydrogenation. Specifically, triple ligands were used to bind Rh3+ ions to form negatively charged coordination complex network, which further combines by electrostatic attraction with positively charged diblock copolymers to obtain Rh3+ ions bound polymer micelles. Following silica deposition onto micelles, calcination and H2 reduction result in hollow mesoporous silica nanoreactors and residence of Rh nanoclusters close to their hollow cavities. Relative to the control silica supported Rh catalysts, the obtained [email protected] show significantly enhanced catalytic activity, cyclohexanol selectivity and stability for phenol hydrogenation. By DFT theoretic calculations and comparison of control experiments, the performance enhancement of [email protected] is ascribed to their unique nanostructures, where the small size of Rh nanoclusters increases the cyclohexanol selectivity by suppressing the formation of cyclohexanone, and the residence of Rh nanoclusters close to hollow cavities enhances their thermal and catalytic stability.